4674-50-4Relevant articles and documents
Preparation of (-)-aristolochene from (+)-valencene: Absolute configuration of (+)-aristolochene from Aspergillus terreus
Cane,Salaski,Prabhakaran
, p. 1943 - 1944 (1990)
The absolute configuration of (+)-aristolochene (1a), isolated from Aspergillus terreus, has been established by direct comparison with a sample of (-)-aristolochene (1b) prepared from (+)-valencene (2).
Highly efficient production of nootkatone, the grapefruit aroma from valencene, by biotransformation
Furusawa, Mai,Hashimoto, Toshihiro,Noma, Yoshiaki,Asakawa, Yoshinori
, p. 1513 - 1514 (2005)
Nootkatone (2), the most important and expensive aromatic of grapefruit, decreases the somatic fat ratio, and thus its demand is increasing in the cosmetic and fiber sectors. A sesquiterpene hydrocarbon, (+)-valencene (1), which is cheaply obtained from Valencia orange, was biotransformed by the green algae Chlorella species and fungi such as Mucor species, Botryosphaeria dothidea, and Botryodiplodia theobromae to afford nootkatone (2) in high yield.
Selective enzymatic synthesis of the grapefruit flavor (+)-nootkatone
Schulz, Sebastian,Girhard, Marco,Gassmeyer, Sarah K.,J?ger, Vera D.,Schwarze, Daniel,Vogel, Andreas,Urlacher, Vlada B.
, p. 601 - 604 (2015)
(+)-Nootkatone is a high-value sesquiterpenoid known for its grapefruit-odor impression. Its isolation from natural plant sources suffers from low yields, and chemical syntheses involve carcinogenic or hazardous compounds. Herein, a biocatalytic route for the synthesis of (+)-nootkatone that combines two enzymes in one pot is presented. In the first step, a cytochrome P450 monooxygenase catalyzes the selective allylic hydroxylation of the sesquiterpene (+)-valencene to the intermediate alcohol nootkatol. In the second step, nootkatol is further oxidized to (+)-nootkatone by an alcohol dehydrogenase (ADH). The challenging task of finding a suitable cofactor regeneration system was solved by careful selection of an appropriate cosubstrate for the ADH, which works in a dual-functional mode. After reaction optimization, involving cosolvent and cosubstrate screening, (+)-nootkatone concentrations of up to 360mg L-1 and a space-time yield of 18mg L-1 h-1 were achieved. Fruitful synthesis: A P450 monooxygenase and an alcohol dehydrogenase are combined in a one-pot cascade to afford the high-value grapefruit flavor (+)-nootkatone by selective oxidation of (+)-valencene.
Manganese complex catalyst for valencene oxidation: The first use of metalloporphyrins for the selective production of nootkatone
DeFreitas-Silva, Gilson,Moreira Meireles, Alexandre,Robles-Azocar, Patrícia,da Silva, Vinicius Santos,de Melo, Carla Nunes
, (2021)
This work describes the oxidation of valencene, a sesquiterpene easily obtained from citrus fruits, and responsible for the fresh odor of oranges. The reactions were catalyzed by manganese porphyrins derived from 5,10,15,20-tetrakis(3,5-dimethoxyphenyl)porphyrin (H2T3,5DMPP): [MnIII(T3,5DMPP)Cl] (MnP1) and [MnIII(Br12T3,5DMPP)Cl] (MnP2), using iodosylbenzene (PhIO), iodobenzene diacetate [PhI(OAc)2], and molecular oxygen as oxidants. The systems MnP1/O2/acetonitrile and MnP1/O2/diethyl carbonate led to higher yields of valencene oxidation products (44% and 48%, respectively) as compared with MnP2 (9% and 7%, respectively), with nootkatone being the major product. The addition of a small amount of imidazole (molar MnP1: imidazole ratio of 1:5) to the MnP1/O2/diethyl carbonate led to superior yields (64%) as compared with systems without the additive. A mechanism for the formation of the two products obtained was also proposed.
Sesquiterpenoids from the fruits of Alpinia oxyphylla and their anti-acetylcholinesterase activity
Chen, Ping,Wang, Pei-Pei,Jiao, Ze-Zhao,Xiang, Lan
, p. 388 - 397 (2014)
Fourteen sesquiterpenoids were isolated from the fruits of Alpinia oxyphylla Miq. Their structures were elucidated based on NMR analyses ( 1H, 13C, DEPT, 1H,1H-COSY, HMQC, HMBC, and NOESY) and identified as 12-nornootkaton-6-en-11-one (3), (+)-(3S,4aS,5R)-2,3,4,4a,5,6-hexahydro-3-isopropenyl-4a,5-dimethyl-1, 7-naphthoquinone (5), nootkatene (6), 9β-hydroxynootkatone (7), 2β-hydroxy-δ-cadinol (8), 4-isopropyl-6-methyl-1-tetralone (11), oxyphyllone E (12), oxyphyllone D (13), oxyphyllanene B (15), oxyphyllone A (16), oxyphyllol E (17), (9E)-humulene-2,3;6,7-diepoxide (18), mustakone (20), and pubescone (21). Among them, 3 was a new norsesquiterpenoid, 8 was a new natural product, and 5, 6, 11, 20, 21 were isolated from A. oxyphylla for the first time. Twenty sesquiterpenoids, 1-5 and 7-21, were investigated for their in vitro acetylcholinesterase (AChE) inhibitory activities, including previously isolated seven sesquiterpenoids from A. oxyphylla, (11S)-12-chloronootkaton-11- ol (1), (11R)-12-chloronootkaton-11-ol (2), nootkatone (4), oxyphyllenodiol A (9), oxyphyllenodiol B (10), 7-epiteucrenone B (14), and alpinenone (19). TLC-Bioautographic assay indicated that 1-4, 7, 14, 16, 18, 19, and 21 displayed anti-AChE activities at 10 nmol. Microplate assay confirmed that 19, 18, 16, and 21 displayed moderate-to-weak anti-AChE activities at the concentration of 100 μM, and 19 was the most potent inhibitor with an IC50 value of 81.6±3.5 μM. The presence of anti-AChE sesquiterpenoids in A. oxyphylla may partially support the traditional use of this fruit for the treatment of dementia. Copyright
METHOD FOR THE MANUFACTURE OF α,β-UNSATURATED KETONES
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Page/Page column 13, (2021/10/30)
A method for the manufacture of an α,β-unsaturated ketone, which method comprises oxidizing an alkene having -CH2- adjacent a carbon-carbon double bond to α,β-unsaturated ketone by passing air or oxygen through a solution of the hydrocarbon containing a catalyst consisting of N-hydroxyphthalimide (NHPI) and cobalt diacetate tetrahydrate at standard temperature and pressure during a period of at least 12 hours.
PROCESS FOR THE PREPARATION OF NOOTKATONE BY USING A IRON (III) PORPHYRIN COMPLEX CATALYST
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Page/Page column 5-7, (2020/12/29)
An allylic oxidation process comprising: forming a mixture containing valencene and an iron (lll)-X porphyrin complex catalyst in a sustainable solvent, introducing molecular oxygen into the mixture, and effecting allylic oxidation to produce nootkatone.
Pd-Catalyzed aerobic oxidation of the sesquiterpene isolongifolene: A green and heterogeneous process
Nunes de Melo, Carla,Robles-Azocar, Patrícia Alejandra,Rodrigues, Yuri Blanc
, (2020/12/25)
The oxidation of the sesquiterpene isolongifolene, catalyzed by Pd/SiO2 prepared through a conventional sol–gel method, resulted mainly in isolongifolen-9-one (65% selectivity), a compound which occupies a prominent place in perfume industry. In addition to the product obtained from the allylic oxidation of isolongifolene, the formation of other oxygenated products with potential industrial application (both total yield of 94%) was also observed. The system can be used for oxidation of other sesquiterpene, valencene. In this case, it was possible to obtain oxygenated products with up to 66% yield. The reactions occurred under mild conditions in a green and heterogeneous oxidation catalytic system. Pd (II) was used as a solo catalyst in the absence of co-oxidants. The catalyst can be easily recovered and re-used maintaining activity and selectivity.
USE OF NOOTKATONE TO TREAT INFECTIONS CAUSED BY NEMATODES, TREMATODES, CESTODES, OR ENDOPARASITIC HELMINTHS
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Paragraph 0173, (2018/10/25)
Compositions and methods for treating and preventing nematode, trematode, cestode, and helminth infestations are disclosed herein.
USE OF NOOTKATONE FOR CONTROLLING PHYTOPATHOGENIC MICROBES
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Paragraph 00408, (2018/12/13)
The application relates to the methods for preventing, treating, or reducing an infection by phytopathogenic, facultative saprophytic or saprotrophic microbes (e.g. phytopathogenic fungi) in crop plants (pre-harvest), or in a crop plant material, or on surfaces in contact with the crop plant material, comprising: contacting them with a composition containing nootkatone and optionally an additional active ingredient; or comprising applying said composition to a vector pest. The application further relates to the compositions comprising nootkatone and optionally an additional active ingredient.
